Chemical protection of metal surface

ABSTRACT

An electrochemical cell includes an anode having a metal material having an oxygen containing layer. The electrochemical cell also includes a cathode and an electrolyte. The anode includes a chemically bonded protective layer formed by reacting a D or P block precursor with the oxygen containing layer.

RELATED APPLICATION

This application claims priority of U.S. Provisional Patent ApplicationsSer. No. 60/713,688 filed Sep. 2, 2005 and Ser. No. 60/739,499 filedNov. 23, 2005, which are incorporated herein by reference.

FIELD OF THE INVENTION

The invention relates to chemical Protection of a metal surface.

BACKGROUND OF THE INVENTION

Electrochemical cells containing a metallic anode, a cathode and a solidor solvent-containing electrolyte are known in the art. Such batterieshave limitations over repeated charge/discharge cycles and may havedrops in their charge and discharge capacity over repeated cycles ascompared to their initial charge and discharge capacity. Additionally,an initial capacity of solid batteries is often less than desirable.There is therefore a need in the art for an improved battery having ahigh initial capacity and maintains such a capacity on repeated chargeand discharge cycles.

Another problem associated with electrochemical cells is the generationof dendrites over repeat charge and discharge cycles. Dendrites may beformed on the anode when the electrochemical cell is charged. Thedendrite may grow over repeated cycles and lead to a reduced performanceof the battery or a short circuit not allowing the charge and dischargeof the battery. There is therefore a need in the art for a battery andelectrode with an improved cycle life and limits the formation of adendrite.

SUMMARY OF THE INVENTION

An electrochemical cell includes an anode having a metal material havingan oxygen containing layer. The electrochemical cell also includes acathode and an electrolyte. The anode includes a chemically bondedprotective layer formed by reacting a D or P block precursor with theoxygen containing layer.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a IR spectroscopy plot of the wavelength versus the intensityfor a lithium metal before and after application of the protectivelayer;

FIG. 2 is a differential scanning calorimetry plot for a lithium metalhaving the protective layer;

FIG. 3 is a diagram of an experimental setup for impedance testing;

FIG. 4 is a plot of the impedance for chlorotrimethylsilane precursorforming a protective layer and a reference material;

FIG. 5 is a plot of the impedance for chlorodiisopropylphosphineprecursor forming a protective layer and a reference material;

FIG. 6 is a plot of the impedance for chlorodiethylphosphine precursorforming a protective layer and a reference material;

FIG. 7 is a plot of the impedance for dromodimethylborane precursorforming a protective layer and a reference material;

FIG. 8 is a plot of the resistance for chlorotrimethylsilane,chlorodiisopropylphosphine, chlorodiethylphosphine, dromodimethylboraneprecursor forming a protective layer and a reference material.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The term electrochemical cell as used herein refers to a device havingan anode, cathode and an ion-conducting electrolyte interposed betweenthe two. The electrochemical cell may be a battery, capacitor or othersuch device. The battery may be of a primary or secondary chemistry. Thebattery may have a solid electrolyte or a liquid electrolyte. The termanode as used herein refers to an electrode, which oxidizes during adischarge cycle.

There is disclosed an electrochemical cell having an anode including ametal material having an oxygen containing layer. The anode metalmaterial may be alkaline metals or alkaline earth metals as indicated inthe periodic table. Non-limiting examples of metal materials include:lithium, aluminum, sodium, and magnesium. In a preferred aspect of theinvention the metal material is lithium.

The oxygen containing layer may be formed by exposing the metal materialto the atmosphere or may otherwise be formed on the metal material. Theelectrochemical cell also includes a cathode, which may be formed of anysuitable material. An electrolyte is interposed between the anode andcathode and may be of any suitable form including solid electrolytesliquid electrolytes and gel polymer electrolytes, which are a polymermatrix swollen with solvent and salt. Solid electrolytes could bepolymer-type, inorganic layer or mixtures of these two. Examples ofpolymer electrolytes include, PEO-based, and PEG based polymers.Inorganic electrolytes could be composed of sulfide glasses, phosphideglasses, oxide glasses and mixtures thereof An example of a liquidelectrolyte includes carbonate solvent with dissolved metal-ion salt,for example 1M LiPF6 in ethylene carbon/diethyl carbonate (EC/DEC).

The anode of the electrochemical cell includes a chemically bondedprotective layer formed thereon by reacting a D or P block precursorwith the oxygen containing layer. The term D or P block precursorincludes compounds that have elements in the D or P block of theperiodic table. Examples of D or P block elements include phosphorus,boron, silicon, titanium, molybdenum, tantalum, vanadium to name a few.The D or P block precursor may be an organo-metallic compound. Examplesof organo-metallic compounds include: inter-metaltic compounds, alloysand metals having organic substituents bonded thereon. In a preferredaspect of the invention D or P block precursors may include silicon,boron or phosphorous. The D or P block precursors react with the oxygencontaining layer of the metal material to form the protective layer.

In one embodiment, the D or P block precursor may be a chemical compoundof the formula: AR¹R²X wherein A is selected from phosphorous or boron,X is a halogen or halogen containing compound and R¹ is selected fromhalogens, alkyl groups having from 1 to 20 carbons, alkoxy groupscontaining 1 to 20 carbons, or aromatic groups having from 1 to 20carbons, R^(2 is) selected from halogens, alkyl groups having from 1 to20 carbons, alkoxy groups containing 1 to 20 carbons, or aromatic groupshaving from 1 to 20 carbons.

The halogen may be chlorine, bromine, fluorine, and iodine. The alkyl,alkoxy, and aromatic groups may be fluorinated or partially fluorinated.

The alcyl group may be methyl, ethyl, n-propyl, isopropyl, n-butyl,isobutyl, sec-butyl, tert-butyl, tert-pentyl, iso-octyl, tert-octyl,2-ethyhexyl, nonyl, decyl, undecyl, cyclopentyl, cyclohexyl,cycloheptyl, cyclooctyl, 1-methylcyclopentyl, 1-methylcyclohexyl,1-methylcyclohexyl, and 1-methyl-4-isopropylcyclohexyl, although otheralkyl groups not listed may be used by the invention. The alkyl groupmay also be functionalized. Suitable functional groups include: ether,sulfide, sulfoxide to name a few.

The aromatic group may be phenyl groups, phenyl groups having alkylsubstituents in the para, meta or ortho position, and polyaromaticcompounds. Examples of suitable polyaromatic compounds includenaphthalene derivatives.

In another embodiment of the invention, the D or P block precursor maybe a chemical compound of the formula: AR¹R² R³ R⁴X wherein A isphosphorous, X is a halogen or halogen containing compound and R¹ isselected from halogens, alkyl groups having from 1 to 20 carbons, alkoxygroups containing 1 to 20 carbons, aromatic groups having from 1 to 20carbons, or oxygen R^(2 is) selected from halogens, alkyl groups havingfrom 1 to 20 carbons, alkoxy groups containing 1 to 20 carbons, aromaticgroups having from 1 to 20 carbons, or oxygen, R3 is selected fromhalogens, alkyl groups having from 1 to 20 carbons, alkoxy groupscontaining 1 to 20 carbons, aromatic groups having from 1 to 20 carbons,or oxygen, R4 is selected from halogens, alcyl groups having from 1 to20 carbons, alkoxy groups containing 1 to 20 carbons, aromatic groupshaving from 1 to 20 carbons, or oxygen.

In the case where the compound includes double bonded oxygen or otherdouble bonded substituent, the number of R groups may be less than fourtotal.

As with the previously described embodiment, the description of thehalogens, alkyl, alkoxy and aromatic groups are the same and are notrepeated.

In another embodiment of the invention, the D or P block precursor maybe a chemical compound of the formula: SiR¹R²R³X wherein, X is a halogenor halogen containing compound and R¹ is selected from hydrogen,halogens, alkyl groups having from 1 to 20 carbons, alkoxy groupscontaining 1 to 20 carbons, or aromatic groups having from 1 to 20carbons, R² is selected from hydrogen, halogens, alkyl groups havingfrom 1 to 20 carbons, alkoxy groups containing 1 to 20 carbons, oraromatic groups having from 1 to 20 carbons R³ is selected fromhydrogen, halogens, alkyl groups having from 1 to 20 carbons, alkoxygroups containing 1 to 20 carbons, or aromatic groups having from 1 to20 carbons.

As with the previously described embodiments, the description of thehalogens, alkyl, alkoxy and aromatic groups are the same and are notrepeated.

EXAMPLES

In the experiments detailed in the examples section, lithium metalstrips were exposed to various precursor compounds. The lithium stripswere placed in a sealed flask at room temperature in an inert atmospherecontaining the precursor compound. The strips were exposed to theprecursor a suitable period of time for the precursor to react with themetal oxygen containing layer on the lithium to form the protectivelayer. Various analysis procedures were performed including: impedancetests, IR spectroscopy tests, and differential scanning calorimetrytests on the various samples.

Example 1

An untreated sample of the lithium metal and a sample treated withchlorotrimethyl silane for 240 seconds according to the above procedurewere analyzed using IR spectroscopy, as shown in FIG. 1. The peakcorrespond to a lithium hydroxide bond is shown in the 3600 cm−1 rangefor the untreated sample. This peak is not shown for the treated samplewhich includes a peak in the 1100 cm−1 range corresponding to a siliconoxygen bond. This relationship indicates the precursor compound hasreacted with the metal oxygen containing to form a silicon oxygen bond.

Example 2

An untreated sample of the lithium metal and a sample treated withchlorotrimethyl silane according to the above procedure were analyzedusing differential scanning calorimetry, as shown in FIG. 2. The sampleswere placed in aluminum pans with nitrogen gas flowing around thesamples. The samples were heated to above the melting point and cooledbelow the melting point repetitively to determine whether the lithiumwas protected from the environment. The untreated lithium sample reactedwith the aluminum pan and did not show melting and solidificationrepresentative of pure lithium metal. The treated sample, as shown inFIG. 2, exhibits very clear melting and solidification of lithium at orvery near the melting point of lithium (the slight amount ofsuperheating or supercooling at the melting point is heating ratedependent). The narrow peaks indicate that the lithium metal isprotected and has not reacted with its environment in contrast to theunprotected sample.

Example 3

Impedance tests were performed on various treated samples of lithium anduntreated lithium as a reference. The experimental setup used is shownin FIG. 3. The various samples were formed using the procedure describedabove. The lithium samples were tested in the experimental setup withthe sample placed in the positive electrode position. The impedanceplots for various samples are shown in FIGS. 4-7. FIG. 4 shows theimpedance plot for a sample treated with a chlorotrimethylsilaneprecursor forming a protective layer. FIG. 5 is a plot of the impedancefor a chlorodiisopropylphosphine precursor forming a protective layer.FIG. 6 is a plot of the impedance for a chlorodiethylphosphine precursorforming a protective layer. FIG. 7 is a plot of the impedance for adibromodimethylborane precursor forming a protective layer. As can beseen in the figures the treated samples all have an impedance curve witha slope less than the reference samples. This behavior indicates animproved performance in comparison to the untreated samples. Theimpedance values were used to calculate a resistance of the varioussamples, which are displayed in FIG. 8 for the various samples. As canbe seen in the figure, the resistance for all the treated samples isless than the untreated reference. The various elements and R groups ofthe precursor material has an affect on the resistance of the samples.The chlorodiisopropylphosphine sample shows the lowest resistance of thetreated samples. A lower resistance metal material is desirable for useas an anode in an electrochemical cell.

The invention has been described in an illustrative manner. It is to beunderstood that the terminology, which has been used, is intended to bein the nature of words of description rather than limitation. Manymodifications and variations of the invention are possible in light ofthe above teachings. Therefore, within the scope of the appended claims,the invention may be practiced other than as specifically described.

1. An anode for an electrochemical cell comprising: a metal materialhaving an oxygen containing layer; a chemically bonded protective layerformed by reacting a D or P block precursor with the oxygen containinglayer.
 2. The anode of claim 1 wherein the D or P block precursor is anorgano-metallic compound.
 3. The anode of claim 1 wherein the metalmaterial is selected from alkaline metals, and alkaline earth metals. 4.The anode of claim 1 wherein the metal material comprises lithium. 5.The anode of claim 1 wherein the D or P block precursor comprises achemical compound of the formula: AR¹R²X wherein A is selected fromphosphorous or boron, X is a halogen or halogen containing compound andR¹ is selected from halogens, alkyl groups having from 1 to 20 carbons,alkoxy groups containing 1 to 20 carbons, or aromatic groups having from1 to 20 carbons, R² is selected from halogens, alkyl groups having from1 to 20 carbons, alkoxy groups containing 1 to 20 carbons, or aromaticgroups having from 1 to 20 carbons.
 6. The anode of claim 5 wherein thehalogen is selected from chlorine, bromine, fluorine, and iodine.
 7. Theanode of claim 5 wherein the alkyl, alkoxy, and aromatic groups may befluorinated or partially fluorinated.
 8. The anode of claim 5 whereinthe alkyl group is functionalized.
 9. The anode of claim 5 wherein thealkyl group is selected from methyl, ethyl, n-propyl, isopropyl,n-butyl, isobutyl, sec-butyl, tert-butyl, tert-pentyl, iso-octyl,tert-octyl, 2-ethyhexyl, nonyl, decyl, undecyl, cyclopentyl, cyclohexyl,cycloheptyl, cyclooctyl, 1-methylcyclopentyl, 1-methylcyclohexyl,1-methylcyclohexyl, and 1-methyl-4-isopropylcyclohexyl.
 10. The anode ofclaim 5 wherein the aromatic group is selected from phenyl groups,phenyl groups having alkyl substituents in the para, meta or orthoposition, and polyaromatic compounds.
 11. The anode of claim 1 whereinthe D or P block precursor comprises a chemical compound of the formula:AR¹R²R³R⁴X wherein A is phosphorous, X is a halogen or halogencontaining compound and R¹ is selected from halogens, alkyl groupshaving from 1 to 20 carbons, alkoxy groups containing 1 to 20 carbons,aromatic groups having from 1 to 20 carbons, or oxygen R² is selectedfrom halogens, alkyl groups having from 1 to 20 carbons, alkoxy groupscontaining 1 to 20 carbons, aromatic groups having from 1 to 20 carbons,or oxygen, R3 is selected from halogens, alkyl groups having from 1 to20 carbons, alkoxy groups containing 1 to 20 carbons, aromatic groupshaving from 1 to 20 carbons, or oxygen, R4 is selected from halogens,alkyl groups having from 1 to 20 carbons, alkoxy groups containing 1 to20 carbons, aromatic groups having from 1 to 20 carbons, or oxygen. 12.The anode of claim 11 wherein the halogen is selected from chlorine,bromine, fluorine, and iodine.
 13. The anode of claim 11 wherein thealkyl, alkoxy, and aromatic groups may be fluorinated or partiallyfluorinated.
 14. The anode of claim 11 wherein the alkyl group isfunctionalized.
 15. The anode of claim 11 wherein the alkyl group isselected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl,sec-butyl, tert-butyl, tert-pentyl, iso-octyl, tert-octyl, 2-ethyhexyl,nonyl, decyl, undecyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl,1-methylcyclopentyl, 1-methylcyclohexyl, 1-methylcyclohexyl, and1-methyl-4-isopropylcyclohexyl.
 16. The anode of claim 1 wherein the Dor P block precursor comprises a chemical compound of the formula: SiR¹R²R³X wherein, X is a halogen or halogen containing compound and R¹ isselected from hydrogen, halogens, alkyl groups having from 1 to 20carbons, alkoxy groups containing 1 to 20 carbons, or aromatic groupshaving from 1 to 20 carbons, R² is selected from hydrogen, halogens,alkyl groups having from 1 to 20 carbons, alkoxy groups containing 1 to20 carbons, or aromatic groups having from 1 to 20 carbons R³ isselected from hydrogen, halogens, alkyl groups having from 1 to 20carbons, alkoxy groups containing 1 to 20 carbons, or aromatic groupshaving from 1 to 20 carbons.
 17. The anode of claim 16 wherein thehalogen is selected from chlorine, bromine, fluorine, and iodine. 18.The anode of claim 16 wherein the alkyl, alkoxy, and aromatic groups maybe fluorinated or partially fluorinated.
 19. The anode of claim 16wherein the alkyl group is functionalized.
 20. The anode of claim 16wherein the alkyl group is selected from methyl, ethyl, n-propyl,isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, tert-pentyl,iso-octyl, tert-octyl, 2-ethyhexyl, nonyl, decyl, undecyl, cyclopentyl,cyclohexyl, cycloheptyl, cyclooctyl, 1-methylcyclopentyl,1-methylcyclohexyl, 1-methylcyclohexyl, and1-methyl-4-isopropylcyclohexyl.
 21. An electrochemical cell comprising:an anode including a metal material having an oxygen containing layer; acathode; an electrolyte,; the anode including a chemically bondedprotective layer formed by reacting a D or P block precursor with theoxygen containing layer.
 22. The electrochemical cell of claim 21wherein the D or P block precursor comprises a chemical compound of theformula: AR¹R²X wherein A is selected from phosphorous or boron, X is ahalogen or halogen containing compound and R¹ is selected from halogens,alkyl groups having from 1 to 20 carbons, alkoxy groups containing 1 to20 carbons, or aromatic groups having from 1 to 20 carbons, R² isselected from halogens, alkyl groups having from 1 to 20 carbons, alkoxygroups containing 1 to 20 carbons, or aromatic groups having from 1 to20 carbons.
 23. The electrochemical cell of claim 21 wherein the D or Pblock precursor comprises a chemical compound of the formula: AR¹R²R³R⁴Xwherein A is phosphorous, X is a halogen or halogen containing compoundand R¹ is selected from halogens, alkyl groups having from 1 to 20carbons, alkoxy groups containing 1 to 20 carbons, aromatic groupshaving from 1 to 20 carbons, or oxygen R^(2 is) selected from halogens,alkyl groups having from 1 to 20 carbons, alkoxy groups containing 1 to20 carbons, aromatic groups having from 1 to 20 carbons, or oxygen, R3is selected from halogens, alkyl groups having from 1 to 20 carbons,alkoxy groups containing 1 to 20 carbons, aromatic groups having from 1to 20 carbons, or oxygen, R4 is selected from halogens, alkyl groupshaving from 1 to 20 carbons, alkoxy groups containing 1 to 20 carbons,aromatic groups having from 1 to 20 carbons, or oxygen.
 24. Theelectrochemical cell of claim 21 wherein the D or P block precursorcomprises a chemical compound of the formula: SiR¹R²R³X wherein, X is ahalogen or halogen containing compound and R¹ is selected from hydrogen,halogens, alkyl groups having from 1 to 20 carbons, alkoxy groupscontaining 1 to 20 carbons, or aromatic groups having from 1 to 20carbons, R^(2 is) selected from hydrogen, halogens, alkyl groups havingfrom 1 to 20 carbons, alkoxy groups containing 1 to 20 carbons, oraromatic groups having from 1 to 20 carbons R³ is selected fromhydrogen, halogens, alkyl groups having from 1 to 20 carbons, alkoxygroups containing 1 to 20 carbons, or aromatic groups having from 1 to20 carbons.